Radical-initiated homo- and copolymerization of cyanomethyl methacrylate

The kinetics of cyanomethyl methacrylate (CyMA) homopolymerization was investigated in acetonitrile with azobisisobutyronitrile as initiator. The rate of polymerization R_p was expressed by R_p = k[AIBN]^0.49[CyMA]^1.2 and the overall activation energy was calculated as 72.3 kJ/mol. Kinetic constants for CyMA polymerization were obtained as follows: k_p/k = 0.10 L^1/2s^?1/2; 2fk_d = 1.57 × 10^?5s^?. The relative reactivity ratios of CyMA(M₂) copolymerization with styrene (r₁ = 0.15, r₂ = 0.29) and methyl methacrylate (r₁ = 0.43, r₂ = 0.75) in acetonitrile were obtained. Applying the Q-e scheme (in styrene copolymerization) led to Q = 1.64 and e = 0.98. The glass transition temperature T_g of poly(CyMA) was observed to be 91°C by thermomechanical analysis. Thermogravimetry of poly(CyMA) showed a 10% weight loss at 265°C in air.     

Thermal analysis of some metal benzohydroxamates

The preparation and thermal analysis of metal chelates of benzohydroxarnic acid (BHA) with Al(III), Cd(II), Co(II), Cu(II) (two compounds), Fe(III), La(III), Pb(II), Mn(II), Ni(II), U(VI) and Zn(II) is discussed. The Al(III), La(III), Pb(II) and Mn(II) chelates are new compounds. DTA and TGA curves of the chelates and of BHA are presented, and the heats of decomposition of the chelates are estimated.     

Artificial red cells with crosslinked hemoglobin membranes

Artificial cells containing concentrated hemoglobin (Hb) solution were prepared by interfacial polymerization of Hb with glutaraldehyde (GA) in liquid membrane capsules (LMC). A solution containing 30% of Hb was emulsified in mineral oil as red cell-size microdroplets, and this emulsion was dispersed in an aqueous phase containing glutaraldehyde to form LMC. The LMC were semipermeable templates that held the microdroplets of Hb in suspension while GA diffused through the oil to the microdroplet surfaces. The GA crosslinked Hb at the surface of each microdroplet to form an artificial red-cell membrane encapsulating Hb solution. A water-soluble surfactant was used to eject the cells from the LMC and suspend them in saline. Several surfactants were evaluated. Cell size was controlled by agitation speed during preparation of the original emulsion. Cells of 2.52 = ±1.69 μm were prepared. The encapsulated Hb retained capacity to bind and release O₂. The cells had aP ₅₀ of 8.9 torr (1200 Pa) and a capacity of 0.55 cc O₂/g of total Hb, indicating that the crosslinked portion of the Hb did not contribute to O₂ transport.     

Statistical mechanical theory of liquid entropy

The multiparticle correlation expansion for the entropy of a classical monatomic liquid is presented. This entropy expresses the physical picture in which there is no free particle motion, but, rather, each atom moves within a cage formed by its neighbors. The liquid expansion, including only pair correlations, gives an excellent account of the experimental entropy of most liquid metals, of liquid argon, and of the hard-sphere liquid. The pair correlation entropy is well approximated by a universal function of temperature. Higher-order correlation entropy, due to n-particle irreducible correlations for n ≥ 3, is significant in only a few liquid metals, and its occurrence suggests the presence of n-body forces. When the liquid theory is applied to the study of melting, we discover the important classification of normal and anomalous melting, according to whether there is not or is a significant change in the electronic structure upon melting, and we discover the universal disordering entropy for melting of a monatomic crystal. Interesting directions for future research are extension to include orientational correlations of molecules, theoretical calculation of the entropy of water, application to the entropy of the amorphous state, and correlational entropy of compressed argon. We clarify the relation among different entropy expansions in the recent literature. © 1994 John Wiley & Sons, Inc.     

Palladium-catalyzed amidation of enol triflates: a new synthesis of enamides

[reaction: see text] The palladium-catalyzed coupling of a range of enol triflates with amides, carbamates, and sulfonamides has been developed. This offers a simple and widely applicable synthesis of enamides, which may not be readily available by other means.     

An investigation into causes and effects of high cyanide levels in the palladium-catalyzed cyanation reaction

[reaction: see text] The palladium-catalyzed cyanation reaction is known to be sensitive to dissolved cyanide. Investigation into some causes of high levels of dissolved cyanide is presented here, along with a robust solution to this problem.     

Study of human urinary metabolism of fenfluramine using gas chromatography-mass spectrometry

The metabolism of (+/-)fenfluramine, 1-(m-trifluoromethylphenyl)-2-N-ethylpropane, an anoretic agent, was investigated in humans. The analysis method was based on the use of ion-exchange resin extraction, solid-phase purification on the Bond Elut1M C8 cartridge, gradient elution high-performance liquid chromatography, enzymic hydrolysis of conjugates, further purification by Bond Elut C8 cartridge, derivatisation and capillary column gas chromatography-mass spectrometry (GC-MS). After administration of a 1 mg kg-1 oral dose, four metabolites plus unchanged fenfluramine were recovered in the 0-24 h urine from human volunteers and characterised by GC-MS. In the conjugated form, fenfluramine, norfenfluramine and m-trifluoromethylhippuric acid were detected by GC-MS. In the aglycone form, the major metabolite, 1-(m-trifluoromethylphenyl)-1,2-propane diol (fenfluramine diol), was monitored using GC-MS. The mass spectral characteristics of the m-trifluoromethylhippuric acid methyl ester, 1-(m-trifluoromethylphenyl)-1,2-propane ditrifluoracetate derivatives and the norfenfluramine and fenfluramine free base obtained under electron-impact ionization are presented. The metabolism of fenfluramine is discussed including a metabolic pathway in man accounting for the formation of its biotransformation products.     

Tunable and coherent radiation in the VUV: high efficiency four-wave difference-frequency mixing in xenon

We report a novel source of tunable, coherent radiation in the vacuum ultraviolet, which use resonantly enhanced difference-frequency mixing in xenon gas Efficiencies are high (o.4%) at modest input laser intensities. With existing dye lasers the range of tunability will span the 152–200 nm region.     

Structure Elucidation of Triterpenoid Saponins Found in an Immunoadjuvant Preparation of Quillaja brasiliensis Using Mass Spectrometry and 1H and 13C NMR Spectroscopy

An immunoadjuvant preparation (named Fraction B) was obtained from the aqueous extract of Quillaja brasiliensis leaves, and further fractionated by consecutive separations with silica flash MPLC and reverse phase HPLC. Two compounds were isolated, and their structures elucidated using a combination of NMR spectroscopy and mass spectrometry. One of these compounds is a previously undescribed triterpene saponin (Qb1), which is an isomer of QS-21, the unique adjuvant saponin employed in human vaccines. The other compound is a triterpene saponin previously isolated from Quillaja saponaria bark, known as S13. The structure of Qb1 consists of a quillaic acid residue substituted with a β-d-Galp-(1→2)-[β-d-Xylp-(1→3)]-β-d-GlcpA trisaccharide at C3, and a β-d-Xylp-(1→4)-α-l-Rhap-(1→2)-[α-l-Arap-(1→3)]-β-d-Fucp moiety at C28. The oligosaccharide at C28 was further substituted at O4 of the fucosyl residue with an acyl group capped with a β-d-Xylp residue.